Meta-hydroxyl-phenyl-arylamino carboxylic acids



Patented Dec. 5, 1933 UNITED STA META-HYDROXYL-PHENYh-ARYLAMiNd CARBOXYLIC ACIDS Leopold Las ka and O skar Haller, Oifenbach-on the-Main, Germany,

assigno'rs to General- Aniline Works, Inc., New York, N, Y., a corporation of Delaware No Drawing. Application November 14,1929,

Serial No. 407,274, and

in. Germany December 6 Claims. (01. 260- 109): I

Our invention relates to new meta-hydroxyphenylarylamine carboxylic acids.

We have found that new meta -hydroxyphenylarylamine carboxylic acids are obtained by heating an alkali salt of a meta-hydroxyphenylarylamine of the formula:

wherein twoXs are hydrogen, and the other Xs stand for hydrogen, halogen, alkyl, alkoxy or aryloxy, with carbon dioxide at an elevated pressure. The reaction may be illustrated by the following probable-equation:

grees, b ut we wish it to be understood that we are not limited to the-particular products or I reaction conditions mentioned therein.

, In autoclave provided with a stirrer, 1850 parts of m-hydroxy-diphenylamine.are dissolved in 560 parts of caustic potash and 3000 parts of water;

the. Water is distilled off in vacuo to complete Wherein two Xs are hydrogen, and the other Xs stand-for hydrogen,halogen, alkyl, alkoxy 0 aryloxy, and Z means an alkali metal.

The position of the carboxylic acid group of these 3 hydroxy phenylarylamine-carboxylic acids is not exactly known. But as the new acids yield, with ferric chloride, a red to violet coloration, it is assumed that the carboxylic group is dryness. After cooling, carbon dioxide is introduced'up to a pressure of 5-10 atmospheres and the temperature is raised to about 150-170.

TES PATENT OFFICE H After heating at this" temperature for 16 hours, 1

the cooled reaction mass is worked up by dissolving it in hot water, filtering the solution containg ing the potassium salt of the formed carboxylic in crtho position to the hydroxyl group and probably in para-position to the NH-group.

The starting materials of our process may be obtained, for instance, by condensing resorcinol with aromatic amines of the benzene series, that is, with aniline and its homologues, alkoxyanilines, aryloxyanilines and the halogen substitution products of these compounds.)

7 The new carboxylicacids are valuablelinterv mediateproducts' for the manufacture of dyestuifs. They are distinguished by a remarkable stability, especially when compared with the carboxylic acids obtained according to the U. S. Patents No. 427,564 and $27,565 these'acids being derived from meta-aminophenol and meta-alkylacid and precipitating-the carboxylic acid by means of dilute hydrochloric acid. The raw carboxylic acid may be purified by dissolving it ina dilute solution of-sodium'carbonate oracetate and againprecipitating it by the addition of an acid. 1 After recrystallization from dilute alcohol it melts at 180-181. Itsalcoholic solution yields, when mixed with a dilute ferric chloride solution, an intensive cherry-medcolon, I t I H h When starting from the sodium salt of "the rn-hydroxy diphenylamine, the process may be carried out in an'analogousimanner.

The following table gives further data relating to other new acids prepared in a quite analogous manner,

Prepared from the condensation Melting gggggg f product from point ride 0 resorclnol and 3.hyd o y-T-methykfiphenylflmine cargl xylic cid o-toluidine 180-182 Violet 3-hydroxy-3-mcthyldiphe sg% e carbo ylic acid mmhfldine 1764770 Violet a-h dmx -4'-methy1diphe y fl carboxylic acid p-to1uidine 1s5-1sa Violet d hen lamine carboxylic m-m 1 200 3hydroxy2 methoxy D Y 0 CH3 OH 0 anls me 199- V1olet NH-OCOOH a-h dmxye y carboxylic OH p'anisidine 175-177" Violet sh drox -z chloro-diphc y mi c ea g ylic acid Mhhmnfline Violet 3-hydroxy-3'-chlor0-dlDh0 y 9c y m-chloroanilinc 189-190 Reddish Cl 011 violet 3-hydmxy-4'-chlom-dipheny e carboxylic acid OH p-ch1or0aniline lass-190 Violet 3-hydroxy-2.4'-dimethyl-diphenylamine carboxylic acid 1.3 dimethy1 4 r1750 Violet CH3 0H amino-benzene g.h d .z"5'-dimethyl-diphenylamine carboxylic acid 1.4 dimethyI-Z- 175-176" Violet CH: CH amino-benzene 3-h dmx -y-methy1-4-methoxydipheny1amine carboxyllc acid 2-methyl-4-amino- 165 Dirty CHa 0H anisole violet s-n droxy-z'-methyl-4-chlor0-diphcnylamine carboxylic acid 5-ch1or0-2-amino- 1so-1s1 Cherry-red CH3 OH toluene a-hydroxy-2-methyl-5'-chl0r0-diphenylamine carboxylic acid "l 4-chloro-2-amino- 208-210 Violet OH; OH toluene 3-hydroxy-3-methy1-4-chlor0-dipheny1amine carboxylic acid 6-chl0ro-3-amln0- 195197 Cherry-red OH; OH toluene Prepared from the condensation Melting product from point tide resorcinol and 3-hydroxy-4-metl1y1-8'-chloro-diphenylamine carboxylic acid z. 1 .4- Oherryqed 01 OH toluene 3-hydroxy-2L4-dichlorodiphenylamine catbc ylic Mid 2.4-dichloro-ani- 215 Cherry-red I 01 OH line 3-hydroxy-3.4'-dichloro-diphenylaminc carboxylic acid 3.4-dichloro-ani- 199 Violet O] OH ine 3-hydroxy-3.4-dicl1loto-6-methyldiphenylamine carbcxylic acid 4.5-dichloro-2-am- 203 Cherry-red 01 OH inc-toluene (lb-Q-NH OOOH 3-hydroxy-4-phenoxy-diphenylamine carboxylic acid p-amino-diphe- 189 Violet OH nyl-ether We claim:

1. As new compounds the meta-hydroxydiphenylamine carboxylic acids of the probable general formula:

X X OH X NEG-C0011,

wherein two Xs are hydrogen, and the other Xs stand for hydrogen, halogen, alkyl, alkoxy or' aryloxy, which compounds are in a dry state crystallized substances being soluble in alkalies, yielding a reddish to violet color by the addition of ferric chloride to their alcoholic solution.

2. As new compounds the meta-hydroxydiphenylamine carboxylic acids of the probable general formula:

wherein Y represents chlorine, a methyl, methoxy or aryloxy group, and X represents hydrogen, chlorine, a methyl, methoxy or aryloxy group, which compounds are in avdry state crystallized substances being soluble in alkalies, yielding a reddish to violet color by the addition of ferric chloride to their alcoholic solution. 1

4. As a new compound the 3-hydroxy-4-chloro-diphenyl-amine-4-carboxylic acid correspond.-

ing to the following probable formula:

which compound is in a dry state a crystallized substance melting at 188-190", soluble in alkalies, gg yielding a violet color by the addition of ferric chloride to its alcoholic solution.

5. As a new compound, the 3-hydroxy-4'- methyl-diphenyl-amine-4-carboxylic acid corresponding to the following probable formula: 25

which compound is in a dry state a crystallized substance melting at 185 C. to 186 C. soluble in alkalies, yielding a violet color by the addition of ferric chloride to its'alcoholic solution.

6. As a new compound, the 3-hydroXy-4'-phenoxy-diphenyl-amine-4-carboxylic acid corresponding to the following probable formula:

oJnOGNHQ-OOOH Y which compound is in a dry state a crystallized substance melting at 189 C., soluble in alkalies,

yielding a violet color by the addition of ferric chloride to its alcoholic solution.

LEOPOLD LASKA.

OSKAR HALLER. 

